Zeolitic Imidazolate Frameworks (ZIFs) owing to their crystalline morphology have well designed pore architecture. ZIFs show great potential for applications in gas separation, gas storage, catalysis and sensors because of their high surface area, pore volume and well defined pore network. In order to utilize ZIFs for aforementioned applications, investigation of pore architecture (pore size, pore size distribution and interconnectivity) of ZIFs in powder or film form is highly essential. Conventional gas adsorption techniques are found to be incapable for providing complete pore architecture of ZIFs due to ultra-microporosity and pressure dependent framework flexibility. In recent years, positron annihilation lifetime spectroscopy (PALS) has been used to investigate the porosity of few ZIFs. In order to establish the applicability of PALS for pore architecture investigation of ZIFs in general, a systematic study for a number of ZIFs (ZIF-67, ZIF-8, ZIF-7l, ZIF-7n ZIF-62, ZIF-90, ZIF-7_0.52-8, Zn_0.25Co_0.75-ZIF-8, and ZIF-8A) have been carried out. These frameworks have been synthesized at room temperature or using solvothermal methods. PALS measurements of these ZIFs confirm the presence of different types of interconnected pores in these frameworks. The estimated pore sizes are compared with the pore sizes determined from other conventional techniques. The present study suggests that PALS is a powerful technique for the investigation of tuning of the pore architecture of all type of ZIFs. The determined pore sizes are the factual average pore size of desolvated bulk ZIF samples free from artifacts. These pore sizes could be correlated with the pore size dependent separation performance of ZIFs.